GOST 27981.1-88

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  ГОСТ 27981.1-88

GOST 27981.1−88 Copper of high purity. Methods of atomic-spectral analysis

GOST 27981.1−88

Group B59

GOSUDARSTVENNYI STANDARD OF THE USSR

HIGH PURITY COPPER

Methods of atomic-spectral analysis

Copper of high purity. Methods of atomic-spectral analysis

AXTU 1709

Valid from 01.01.1990
until 01.01.2000*
_______________________________
* Expiration removed
Protocol N 7−95 Interstate Council
for standardization, Metrology and certification
(IUS N 11, 1995). — Note the manufacturer’s database.

INFORMATION DATA

1. DEVELOPED AND INTRODUCED by the Ministry of nonferrous metallurgy of the USSR

PERFORMERS:

Kopanev A. M., E. N. Gilbert, L. N. Shabanova, G. L. Buchbinder, N. To. Baicheva, I. I. Tarasova, V. T. Yatsenko, N. In. Prokopenko, L. V., Bandyk, B. M. Rogov, E. N. Gazalov, I. I. Lebed

2. APPROVED AND put INTO EFFECT by Decision of the USSR State Committee for standards from 22.12.88 N 4443

3. The term of the first check — 1994

The frequency of inspection — 5 years

4. INTRODUCED FOR THE FIRST TIME

5. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS

This standard specifies the atomic spectrometry methods (atomic emission-inductively coupled plasma as the excitation source spectrum and atomic absorption with flame and electrothermal atomization) of the definition of mass fractions of impurities in high purity copper with branch basics substochiometric extraction with di-2-ethylhexyladipate acid or electrolysis.

1. GENERAL REQUIREMENTS

1.1. General requirements for methods of analysis and safety requirements when performing tests according to GOST 27981.0 with the Supplement.

Mass fraction of impurities in high purity copper by these methods determined in parallel in three batches.

2. THE METHOD OF SEPARATION OF COPPER SUBSTOCHIOMETRIC EXTRACTION

The method consists of dissolving the sample of copper in a mixture of hydrochloric acid and hydrogen peroxide, the separation of copper from impurities by extraction substochiometric di-2-ethylhexylphthalate acid and identifying in the raffinate atomic emission method with inductively coupled plasma or atomic absorption method with electrothermal and flame atomizers the following elements in the ranges of mass fraction ·10%:

Allowed the determination of aluminum (0,8−10)·10% and magnesium (1.0 to 10)·10%.

2.1. Equipment, reagents, solutions

Installation for atomic emission analysis of the type RI 8490 or similar, for example, ARL 3580.

Spectrophotometer atomic absorption the Perkin-Elmer model 503 that allow for flame and electrothermal atomization of samples; or similar (such as the company Hitachi, model 180−80).

Electrothermal atomizer type HGA-76 or similar type.

Recorder Perkin-Elmer 56 or similar.

Argon gaseous and liquid GOST 10157 (the highest grade).

Acetylene, dissolved and gaseous technical GOST 5457.

The air compressed under a pressure of 2·10-6·10PA (2−6 kg/cm).

Lamps hollow cathode for aluminium, bismuth, iron, cadmium, cobalt, silicon, magnesium, manganese, copper, Nickel, lead, antimony, chromium, zinc, tin.

Electrodeless lamp for arsenic.

Oscillator for electrodeless lamps.

Burner with a slit length of 100 mm.

Footwear of any type of the 2nd accuracy class with the error of weighing according to GOST 24104*.
_______________
* On the territory of the Russian Federation GOST 24104−2001, here and hereafter. — Note the manufacturer’s database.

Technical scale with a weighing error in the attached passport.

Electromechanical scrambler type TU-2 or the apparatus for mixing liquids, for example, of the type AVB-4P or a similar type.

Tile electrical with closed spiral.

Glass N-1−100 TCS according to GOST 25336.

Glass-1−100 TCS according to GOST 25336.

Flask conical KN-2−2000 TCS according to GOST 25336.

Funnel conical In-36−80 TC GOST 25336.

Funnel separating VD-1−100 HS; VD-3−2000 TC GOST 25336.

Glass cover (or lid porcelain).

Beaker is 50 (1000) according GOST 1770.

Volumetric flasks 2−2000−2 according GOST 1770.

Volumetric flasks 2−10−2, 2−50−2 according GOST 1770.

Vials P-2−10−14/23 KHS GOST 1770.

Pipette 8−2-0,2 according to GOST 20292*.
________________
* On the territory of the Russian Federation there are 29169−91 GOST, GOST 29227−91−29229−91 GOST, GOST 29251−91-GOST 29253−91, here and hereafter. — Note the manufacturer’s database.

Pipette 5−2-1, 5−2-2, 5−5-2, 5−10−2 according to GOST 20292.

Bowl platinum according to GOST 6563.

Nitric acid of high purity according to GOST 11125 and diluted 1:6, 1:10, 1:2.

Hydrochloric acid of high purity according to GOST 14261 and diluted 1:1, 1:2, 1:3, 1:2,5; 1:10.

Mixture of nitric and hydrochloric acids: mixed nitric and hydrochloric acids in a ratio (1:3).

Hydrogen peroxide high purity (stable product).

Potassium hydroxide according to GOST 24363, an aqueous solution of 4 mol/DMsolution of 2 mol/DMin the mixture ethanol-water (2:1).

Hexane.

Di-2-ethylhexyladipate acid (di-2-EHDHFK).

9 sodium silicate and water according to normative-technical documentation.

The technical rectified ethyl alcohol according to GOST 18300.

Bismuth GOST 10928* brand Vi00.
______________
* On the territory of the Russian Federation GOST 10928−90. — Note the manufacturer’s database.

The restored iron or iron powder according to GOST 9849.

Cation exchange resin KU-2−8 according to GOST 20298.

Sodium hydroxide according to GOST 4328, a solution of 400 g/DM.

Tin GOST 860 brand 00.

Potassium phosphate according to GOST odnosemjannyj 4198.

Potassium dichromate according to GOST 4220.

Cadmium GOST 1467* grade not lower KD 0.
______________
* On the territory of the Russian Federation GOST 1467−93, here and hereafter. — Note the manufacturer’s database.

Cobalt GOST 123* stamps K0.
______________
* On the territory of the Russian Federation GOST 123−98 (01.07.2009 valid GOST 123−2008), here and hereafter. — Note the manufacturer’s database.

Silicon dioxide according to GOST 9428.

Manganese metal according to GOST 6008* brand Mr 00.
______________
* On the territory of the Russian Federation GOST 6008−90, here and hereafter. — Note the manufacturer’s database.

Copper according to GOST 859* brand M0k.
______________
* On the territory of the Russian Federation GOST 859−2001, here and hereafter. — Note the manufacturer’s database.

Arsenic metal.

Arsenious anhydride according to GOST 1973.

Nickel GOST 849* stamps D0.
______________
* On the territory of the Russian Federation GOST 849−97 (01.07.2009 standards 849−2008), here and hereafter. — Note the manufacturer’s database.

Lead according to GOST 3778* mark S.
______________
* On the territory of the Russian Federation GOST 3778−98, here and hereafter. — Note the manufacturer’s database.

Antimony GOST 1089 grade not lower su 000.

Chrome metal according to GOST 5905*.
______________
* On the territory of the Russian Federation GOST 5905−2004. — Note the manufacturer’s database.

Zinc GOST 3640* grade not lower than C 1.
______________
* On the territory of the Russian Federation GOST 3640−94, here and hereafter. — Note the manufacturer’s database.

Tellurium of high purity according to normative-technical documentation.

Standard samples for composition of copper.

2.2. Preparations for the analysis

2.2.1. Preparation of standard solutions of the identified elements

2.2.1.1. Bismuth: bismuth weighed weight 0,100 g dissolved in 5 cmof nitric acid. The resulting solution was placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with water.

1 cmof the solution contains 1 mg of bismuth.

2.2.1.2 Iron

Solution a: a sample of iron weighing 0,100 g dissolved in 2 cmof hydrochloric acid with the addition of 0.5 cmof nitric acid. The resulting solution was placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with water.

1 cmof the solution contains 1 mg of iron.

Solution B: aliquot part of the solution And a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof a solution contains 0.1 mg of iron.

Solution: aliquot part of a solution with a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 0.01 mg of iron.

2 2.1.3 Cadmium

Solution a: the weight of cadmium weight 0,100 g dissolved in 5 cmof hydrochloric acid diluted 1:1. The resulting solution was placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 1 mg of cadmium.

Solution B: aliquot part of the solution And a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof a solution contains 0.1 mg of cadmium.

Solution: aliquot part of a solution with a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 0,

01 mg of cadmium.

2.2.1.4 Cobalt

Solution a: a sample of cobalt by weight 0,100 g dissolved in 5 cmof nitric acid. The resulting solution was transferred to a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 1 mg of cobalt.

Solution B: aliquot part of the solution And a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof a solution contains 0.1 mg of cobalt.

Solution: aliquot part of a solution with a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 0.01 mg cobalt

TA.

2.2.1.5. Manganese

Solution a: a portion of the manganese weight 0,100 g dissolved in 5 cmof hydrochloric acid. The resulting solution was transferred to a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 1 mg of manganese.

Solution B: aliquot part of the solution And a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof a solution contains 0.1 mg of manganese.

Solution: aliquot part of a solution with a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 0.01 mg Margan

CA.

2.2.1.6. Arsenic

Solution a: a portion of the arsenic mass dissolve 0,100 g in a mixture of 5 cmof hydrochloric acid and 2 cmof nitric acid when heated. The resulting solution was transferred to a volumetric flask with a capacity of 100 cmand adjusted to the mark with water.

1 cmof the solution contains 1 mg of arsenic.

The same solution can be prepared from arsenious anhydride. For this purpose a portion of the anhydride by weight of 1,320 g is placed in a measuring flask with volume capacity of 1000 cm, flow 10 cmof sodium hydroxide solution, stirred to dissolve the sample and adjusted to the mark with water.

Solution B: aliquot part of the solution And a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof a solution contains 0.1 mg of arsenic.

Solution: aliquot part of a solution with a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 0.01 mg we

Shaka.

2.2.1.7. Copper (M1): a sample of copper with a mass of 5.00 g dissolved in 20−25 cmof nitric acid when heated. The resulting solution was placed in a volumetric flask with a capacity of 50 cmand was adjusted to the mark with water.

1 cmM1 of solution contains 100 mg of copper.

Copper (M2): a sample of copper with a mass of 5.00 g dissolved in a mixture of 30 cmof hydrochloric acid and 50 cmof a 30% solution of hydrogen peroxide added in portions of 5 cm. The solution is heated to boiling, boil for 2−3 min to remove residual peroxide, cooled, placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with water.

1 cmof solution M2 contains 50 mg med

I.

2.2.1.8. Nickel

Solution a: a portion of the Nickel weight 0,100 g dissolved in 5 cmof nitric acid when heated. The resulting solution was placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with water.

1 cmof the solution contains 1 mg of Nickel.

Solution B: aliquot part of the solution And a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof a solution contains 0.1 mg of Nickel.

Solution: aliquot part of the solution B of Nickel with a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cm, adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 0.01 mg Nike

La.

2.2.1.9. Tin: the weight of tin weight 0,100 g dissolved in 5 cmof hydrochloric acid with the addition of 2−3 drops of nitric acid. The resulting solution was placed in a volumetric flask with a capacity of 100 cm, adjusted to the mark with hydrochloric acid diluted 1:2.

1 cmof the solution contains 1 mg of tin.

2.2.1.10. Lead

Solution a: a sample of lead weighing 0,100 g dissolved in 5 cmof nitric acid, diluted 1:6, and the solution transferred to a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 1 mg lead.

Solution B: aliquot part of the solution And of lead of 10 cmis placed in a volumetric flask with a capacity of 100 cm, adjusted to the mark with nitric acid, diluted 1:10.

1 cmof a solution contains 0.1 mg of lead.

Solution: aliquot part of a solution of lead of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 0.01 mg pig

CA.

2.2.1.11. Antimony

Solution a: a portion of the antimony by weight 0,100 g dissolved in 10 cmof a mixture of hydrochloric and nitric acids (3:1) under heating, after removal of the nitrogen oxides and the solution transferred to a volumetric flask with a capacity of 100 cmand adjusted to the mark with hydrochloric acid diluted 1:2.

1 cmof the solution contains 1 mg of antimony.

Solution B: aliquot part of the solution And antimony of 10 cmis placed in a volumetric flask with a capacity of 100 cm, adjusted to the mark with nitric acid, diluted 1:10.

1 cmof a solution contains 0.1 mg of antimony.

Solution: aliquot part of a solution of antimony in a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cm, adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 0.01 mg sure

we.

2.2.1.12. Tellurium: tellurium weighed weight 0,100 g dissolved in 5 cmof nitric acid and evaporated to dryness. The dry residue is dissolved in 10 cmof sodium hydroxide solution, dilute with water and add 20 cmof hydrochloric acid. The solution was transferred to a volumetric flask with a capacity of 100 cmand adjusted to the mark with water.

1 cmof the solution contains 1 mg of tellurium.

2 2.1.13. Phosphorus

Solution a: a sample mass of potassium phosphate 0,4387 g dissolved in 50 cmof water, the solution transferred to a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 1 mg of phosphorus.

Solution B: aliquot part of the solution And a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof a solution contains 0.1 mg of phosphorus.

Solution: aliquot part of the solution of phosphorus In a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cm, adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 0.01 mg

phosphorus.

2.2.1.14. Chrome

Solution A. Method 1: a suspension of potassium dichromate mass 2,8269 g dissolved in 100 cmof water. The solution is transferred into a measuring flask with volume capacity of 1000 cmand was adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 1 mg of chromium.

Method 2: a sample of chromium weighing 0,100 g dissolved in 5 cmof hydrochloric acid by heating on a water bath. The resulting solution was placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with water.

Solution B: aliquot part of the solution And chromium of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof a solution contains 0.1 mg of chromium.

Solution: aliquot part of a solution of chromium of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 0.01 mg x

Roma.

2.2.1.15. Zinc

Solution a: a sample of zinc weight 0,100 g dissolved in 5 cmof nitric acid, diluted 1:2. The resulting solution was transferred to a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 1 mg of zinc.

Solution B: aliquot part of the solution And zinc with a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof a solution contains 0.1 mg of zinc.

Solution: aliquot part of a solution of zinc with a volume of 10 cmis placed in a volumetric flask with a capacity of 100 cmand adjusted to the mark with nitric acid, diluted 1:10.

1 cmof the solution contains 0.01 mg of CIN

ka.

2.2.1.16. Copper: a sample of copper weighing 1,000 grams is placed in a beaker with a capacity of 100 cmand dissolved by heating in 20 cmof nitric acid, diluted 1:1, and the solution heated to boiling, cooled, transferred to a volumetric flask with a capacity of 100 cmand adjusted to the mark with water.

1 cmof solution contains 10 mg of copper.

2.2.1.17. Silicon GOST 4212.

2.2.2. Preparation of multi-element standard solutions (MES)

2.2.2.1. Solution 1 MES

In a volumetric flask with a capacity of 100 cmis introduced to 15 cmof hydrochloric acid and 2 cmof standard solutions And of bismuth, cadmium, cobalt, manganese, tin, tellurium, chromium and adjusted to the mark with water. 1 cmof a solution of MES 1 contains 20 ág of bismuth, cadmium, cobalt, manganese, tin, tellurium, and chromium.

2.2.2.2. A solution of MES 2

In a volumetric flask with a capacity of 100 cmis introduced to 15 cmof hydrochloric acid and 2 cmof standard solutions And of iron, silicon, arsenic, Nickel, lead, zinc, antimony and bring to the mark with water. The solution was stored in a plastic container. 1 cmMES solution 2 contains 20 g of iron, silicon, arsenic, Nickel, lead, antimony and zinc.

2.2.2.3. Solution MES 3

In a volumetric flask with a capacity of 100 cmis introduced 5 cmof a mixture of MES 1 and adjusted to the mark with nitric acid, diluted 1:10. 1 cmof the solution of the MEA 3 contains 1 µg of bismuth, cadmium, cobalt, manganese, tin, tellurium, and chromium.

2.2.2.4. a. Solution MES 4

In a volumetric flask with a capacity of 100 cmis introduced to 15 cmof hydrochloric acid and 5 cmof a mixture of MES 1, 5 cmstandard solution And zinc, and is adjusted to the mark with water. 1 cmof a solution of MES of 4 contains 1 µg of bismuth, cadmium, cobalt, manganese, tin, tellurium, chromium, and 50 mg of zinc.

2.2.3. Preparation and certification of synthetic blend

In a glass with a capacity of 100 cmwas placed 1,000 g of a standard sample of composition of copper 1921Х (or samples of copper containing cadmium, cobalt, tellurium, chromium not more than 1·10%). The chips are washed with 5−10 cmof hydrochloric acid diluted 1:10, and then double-deionized water.

In glass injected 0.3 cmof a solution of MES 4 and just 6 cmof hydrochloric acid. Cover glass (or cover) and injected 3−4 cmof 30% hydrogen peroxide solution. After 20 minutes add another 4−6 cmof peroxide. After dissolution of the sample Cup put on a tile solution bring to the boil and after 2−3 minutes the glass is removed from the tile and cool the solution. The prepared mixture contains 1000 mg copper, 15 mg of aluminium and zinc and 0.3 µg of cadmium, cobalt, tellurium, chromium. The error due to the preparation of the mixture should not exceed 5%. The mixture is used to check the correctness of the results of analysis in the determination of cadmium, cobalt, tellurium, chromium

.

2.2.4. Preparation of solutions comparison

Series 1: solutions N 1−3 to account for the spectral interference from copper.

Three volumetric flasks with a capacity of 50 cmis placed 1,0; 1,5 and 2,5 cmof a standard solution of copper M1 (p.2.2.1.7) and adjusted to the mark with nitric acid, diluted 1:10. Solutions contain 2, 3 and 5 mg/cmof copper.

Series 2: 4−11 N the solutions for constructing the calibration graphs.

Five volumetric flasks (N 4−8) with a capacity of 50 cmplaced respectively 0,20; 0,50; 1,25; 2,50 and 5,00 cmof a solution of MES 3 and 0,10; 0,25; 0,50; 1,25; 2,50 cmof a solution of MES 2. Three volumetric flasks (N 9−11) with a capacity of 50 cmis placed 0,50; 1,25; 2,5 cmof a solution of the MEA 1.

All flasks are poured 1 cmof a standard solution of copper M1 (p.2.2.1.7) and adjusted to the mark with nitric acid, diluted 1:10. Solutions N 4−8 contain, respectively, by 0,004; 0,010; 0,020; 0,050; 0,100 µg/cmof bismuth, cadmium, cobalt, manganese, tin, tellurium, chromium and 0.04; 0,10; 0,25; 0,50; 1,00 µg/cmiron, silica, arsenic, Nickel, lead, antimony and zinc. Solutions N 9, 10, 11 contain 0,25; 0,50; 1,0 µg/cmof bismuth, cadmium, cobalt, manganese, tin and chromium. Solutions N 4−11 contain 2 mg/cm

copper.

2.2.5. Cleaning technical di-2-EHDHFK

In a separating funnel with a capacity of 2000 cmis placed 300 cmtechnical di-2-EHDHFK and 450 cmhexane. Add 750 cm4 M potassium hydroxide solution. The contents of the separating funnel mix. This separating funnel is inverted up-and-down 3−7 times, each time releasing the air from a crane, and fix it in the Electromechanical shaker, the contents stirred for 10 min.

After separation the aqueous layer (lower) was separated and discarded. In the separatory funnel is introduced the 750 cmof hydrochloric acid diluted 1:2.5, and conducting operations on the content stirring separating funnel. The aqueous layer (lower) was separated and discarded. The funnel is administered 750 cmof water and repeat the operation of stirring the content of separating funnel. The aqueous layer (lower) was separated and discarded.

In the separatory funnel is introduced 790 cm2M potassium hydroxide solution. Gently flip separatory funnel up and down 5−10 times, each time releasing the air out of it. Using the scrambler stirred the contents of the funnel 10 min. See Department of the hexane (upper) layer. The bottom layer, which is a solution of the potassium salt of di-2-EHDHFK in a mixture water-alcohol-hexane is poured into a flask with a capacity of 2000 cm.

The hexane layer is discarded and the solution of the potassium salt of di-2-EHDHFK returned to the separatory funnel. It is administered 200 cmof hexane and shaken for 10 min. the Separated hexane layer (upper) is discarded. Water-alcohol-hexane layer is injected in a separatory funnel and treated with 750 cmof hydrochloric acid diluted 1:3 by shaking for 5 min the Aqueous layer (bottom) is discarded and the organic layer was washed with 750 cmof hydrochloric acid diluted 1:3 for 5

min.

2.2.6. The establishment of the volume of the solution of di-2-EHDHFK required to substochiometric extraction

In a separating funnel with a capacity of 100−150 cmis introduced 20 cmM2 mortar (n.2.2.1.7) and 24.5 cmof a solution of purified di-2-EHDHFK, perform the extraction of copper for 15 min, the raffinate is separated and determine the content therein of copper by any method, for example atomic absorption in the flame «acetylene-air».

1 cmof the raffinate should contain 2−3 mg of copper. Otherwise, the extraction is carried out again by changing accordingly (increasing or decreasing) the amount of the used extractant. Thus, set the volume of the solution of di-2-EHDHFK (), wherein the concentration of copper remaining in the raffinate is 2−3 mg/cm.

2.3. Analysis

2.3.1. Dissolution samples

A portion of the sample of copper with a mass of 1,000 g in the form of chips or powder is placed in a beaker with a capacity of 100 cm. To remove surface contamination, the sample is washed once with 5−10 cmof hydrochloric acid diluted 1:10 and double-deionized water. To the beaker was added 12 cmof hydrochloric acid, covered with glass and injected 3−4 cmof 30% hydrogen peroxide solution. 20 min after completion of the reaction add another 4−6 cmof peroxide. This amount of peroxide sufficient for almost complete dissolution of copper; otherwise, add 2−5 cmof peroxide. 30 minutes after dissolution of the sample Cup put on the tiles, the solution is heated to boiling and cooled.

2.3.2. Separation of copper

Glass glass is removed and the solution is quantitatively transferred to a separating funnel with a capacity of 100−150 cm, using a 5−7 cmwater. The funnel is injected hexane solution of di-2-EHDHFK, the amount established in paragraph 2.2.6. Extracted copper for 15−20 min., the raffinate is separated and transferred back to the glass.

2.3.3. Preparation of the raffinate to the instrumental analysis

The raffinate is evaporated at a temperature of 80−85 °C to wet salts and then dissolve them in 4−5 cmof nitric acid, diluted 1:10. The solution was transferred into a test tube with divisions and adjusted to a volume of 10 cmof nitric acid, diluted 1:10.

2.3.4. The control experience

In a glass with a capacity of 100 cmis introduced 6 cmof hydrochloric acid and 12 cmof 30% hydrogen peroxide solution. The contents of the beaker is evaporated at a temperature of 80−85 °C. to the syrupy state. In a glass introduced 4−5 cmof nitric acid, diluted 1:10. The resulting solution was placed in a vial with graduations up to 10 cmand the volume was adjusted to 10 cmof nitric acid, diluted 1:10. Carrying out of experiences on the standard samples of composition of copper.

2.3.5. Analysis of atomic emission spectrometer with inductively coupled plasma

2.3.5.1. Installation of PU 8490 (or similar) is prepared to work in accordance with the manual. Set the operating mode of the plasma source: argon pressure at the inlet of the source is 3·10PA (3 kgf/cm); the flows of argon: coolant — 16 DM/min, auxiliary — 0.2 DM/min transporting the aerosol sample 1 DM/min; power supplied to the plasma, to 1.2 kW, the height of the radar emissions to 15 mm; the feed rate of the solution — 2.3 cm/min. integration Time is 10 s, the PMT voltage for all elements — 1000 V for copper — 800 V.

The measurements were carried out 30 minutes after switching on the device.

Analytical lines of the determined elements and working conditions of atomic-emission spectrometer are given in table.1.

By means of a peristaltic pump and the spray gun is introduced into the plasma high-frequency discharge consistently water, solutions checklist experience, solutions comparisons 1−3 N, then N is 4, 6, 8, 10, 11 and refined solutions of the analyzed samples. Measure the magnitude of the analytical signals of elements in the relevant channels of the spectrometer. For each solution, the measurements were carried out twice.

2.3.5.2. Calculation of concentrations of the determined elements in copper is carried out on a computer under the special program, the scheme which used the formula given below.

Table 1

Notes:

1. Analytical lines of the determined elements may be provided in quantometer device or output from a monochromator or scanning spectrometer channel.

2. Allowed the use of cadmium analytical line 228,802 nm; for manganese — 259,373 nm.

3. If the vacuum quantometer, arsenic is used in line 189,042 nm.

4. Do not use the analytical line zinc 213,856 nm.


Mass fraction of the element in the sample of copper () in percent is calculated by the formula

, (1)

where is the concentration of the element in the raffinate of the sample of copper, µg/cm;

 — concentration in solution in the reference experiment, µ g/cm;

 — ratio of sample samples of copper and final volume of the raffinate is 10 to 1,000 mass of sample g %.

The concentration of each analyzed element in the solution of the control experiment (), µg/cm, calculated by the formula

, (2)

where is the concentration of the element in solutions comparison N 4, 6, 8, µg/cm;

, , , is the measured value of the signal in the channel of the element in solution in the reference experiment, water solution, comparison N 1 and in solutions comparison N 4, 6, 8, mV.

The concentration of the element in the raffinate (), µg/cm, calculated by the formula

, (3)

where , is the concentration of the element in the raffinate and in solutions comparison N 4, 6, 8, µg/cm;

, , is the measured value of the signal in the channel of the element in the raffinate solution of N 1 comparisons and solutions for comparison, N 4, 6, 8, mV;

 — the value of the spectral interference from copper on the designated elements.

The value of the signal spectral interference from copper to identify the elements remaining in the raffinate (), mV, is calculated by the formula

, (4)

where , , is the concentration of copper remaining in the raffinate (found by the formula 5), in solutions (N 1, 2 or 3), a smaller and more towards , mg/cm;

, , is the measured value of the signal in the channel of the element in a solution of comparison 1 and N in solution comparison with the concentration of copper and , mV.

Note. If the concentration of copper remaining in the raffinate 1.6 g/DM, the calculation of concentrations of bismuth, arsenic, tin, lead, antimony, in that the raffinate is not carried out.


The concentration of copper remaining in the raffinate , mg/cm, calculated by the formula

, (5)

where , is the concentration of copper remaining in the raffinate and solutions for comparison, N 1, 2, and 3, mg/cm;

, , is the measured value of the signal of copper in the raffinate, water and solutions comparison N 1, 2, and 3 mV.

2.3.5.3. Allowable absolute differences between the highest and lowest results of three parallel measurements at a confidence level =0.95 is (the rate of convergence) and the results of the analysis of the same samples obtained in two laboratories and one reference laboratory, but under different conditions (a measure of reproducibility) shall not exceed the values given in table.2.

Table 2

For intermediate values of the mass fraction of the elements of the calculation and is carried out by linear interpolation.

The final result of the analysis be the arithmetic mean of three definitions, each of which is obtained in two dimensions.

2.3.6. Analysis on atomic absorption spectrophotometer

2.3.6.1. Electrothermal atomization

Apparatus and electrothermal atomizer (ETA) is prepared to work in accordance with the operating instructions. Conditions for atomic absorption measurement are given in table.3. After switching to the network focus lamp and heated it for 15−20 min THIS is administered sequentially refined, solutions in the reference experiment and the solutions comparison is carried out, the mode of atomization and register analytical signals of elements. The measurement procedure is carried out twice.

Table 3

Notes:

1. The volume aliquote part of the solution, enter in THIS, is 0.02 cm. It can be increased to 0.05 cm. In this case, the drying time was 30 s.

2. When using other brands of instruments operation and measurement conditions select the separately.

3. The atomization is carried out at stopped flow.


Mass fraction of the element in percent is calculated by the formula (1).

The results of the measurements are refined, solutions in the reference experiment and compare the solutions N 1, 4−8 determine the concentration of elements in the refined and solutions in the reference experiment according to the formula

, (6)

where , , , is the concentration of the element in the raffinate, a control experiment, in a smaller and more in relation to and comparison of solutions (N 1, 4−8), ug/cm;

, , ,  — the average value of the peak absorption of the element in the raffinate, a control experiment, in solutions comparison with concentrations of the analyzed element and , mm.

Allowable absolute differences between the highest and lowest results of three parallel measurements at a confidence level =0.95 is (the rate of convergence) and the results of the analysis of the same samples obtained in two laboratories and one reference laboratory, but under different conditions (the rate of convergence) must not exceed the values given in table.4.

Table 4

For intermediate values of the mass fraction of the elements of the calculation and is carried out by linear interpolation.

2.3.6.2. Atomization in flame «acetylene-air"

The device is prepared to work in accordance with the manual. Measurement conditions are given in table.5.

Table 5

Notes:

1. Odnoschelevye burner, the length of the slit is 100 mm.

2. Air consumption — 21,6 DM/min, acetylene and 3.2 DM/min.


For analysis after inclusion of the device in the network focus lamp hollow cathode. After warming up of lamp during 10−15 minutes light the flame «acetylene-air» and spraying it with a solution comparison N 8 choose the position of the burner and the rate of spraying of the solution, providing maximum atomic absorption analytical line of the element. In chosen in such a way conditions is sprayed into the flame refined, the solutions in the reference experiment and compare the solutions N 1, 5, 6, 7, 8, 9, 10, recording signals the recorder «Perkin-Elmer"-56. The measurement of each solution repeated twice and calculated the average arithmetic value of signal.

The results of the measurements are refined, solutions control experience and solutions comparison N 5−8 calculated mass fraction of element in sample of copper by the formulas (1) and (6).

Allowable absolute differences between the highest and lowest results of three parallel measurements at a confidence level =0.95 is (the rate of convergence) and the results of the analysis of the same samples obtained in two laboratories and one reference laboratory, but under different conditions (a measure of reproducibility) shall not exceed the values given in table.6.

Table 6

For intermediate values of the mass fraction calculation and is carried out by linear interpolation.

2.3.6.3. Control of the correctness of the results of the analysis carried out using certified reference materials certified copper or a mixture prepared according to claim 2.2.3, in which the certified value of the mass fraction of each of the identified elements is different from the mass fraction of that element in the sample not more than two times.

Use addition method in accordance with GOST 25086.

The tests are considered valid if reproduced the mass fraction of this component in the standard sample or in a certified mixture differs from the certified characteristics are not more than 0.71, the value of which is given in table.4 and 6.

3. METHOD WITH ELECTROCHEMICAL SEPARATION OF COPPER

The method consists of dissolving the sample in nitric acid, separation of copper by electrolysis and the electrolyte definition in the atomic emission method with inductively coupled plasma or atomic absorption method with electrothermal atomizer of the elements in the ranges of mass fraction ·10%:

Allowed determination of magnesium (1−20)·10%.

3.1. Equipment, reagents, solutions

Installation for atomic-emission analysis according to claim 2.1.

Polarized atomic absorption spectrophotometer with electrothermal atomizer, for example, firms Hitachi.

Footwear of any type of the 2nd accuracy class with the error of weighing according to GOST 24104.

Installation for the distillation of acids (Fig.1) or other type (in quartz apparatus).

Damn.1. Installation for the distillation of acids

1 — funnel; 2 — heater; 3 — refrigerator; 4 — valve for filling acid; 5 — flask; 6 — drain acid; 7 — flask

Damn.1

Damn.2. Installation for electrolysis, powered by DC

Installation for electrolysis powered by DC (Fig.2), or another type.

1 — screw-locking the electrode; 2 — cocobod; 3 — screw-clamp holder; 4 — bus; 5 — flexible cable; 6 — holder; 7 — hole electrode; 8 — stand; 9 — the case of Plexiglas

Damn.2

Plastic cans with lids with capacity of 250 cm.

Funnel IN-56−105ХС according to GOST 25336.

Volumetric flasks 2−100−2 according GOST 1770.

Beakers 25; 100 GOST 1770.

Pipettes 2−2-1, 2−2-5, 2−2-20, 2−2-50, 4−2-1, 4−2-20, 5−2-1, 6−2-5, 6−2-10, 7−2-5, 7−2-10 according to GOST 20292.

Vials P-2−10−0,1 KHS GOST 1770.

Test tube PP-20-SH 10/19 GOST 19908*.
______________
* On the territory of the Russian Federation GOST 19908−90, here and hereafter. — Note the manufacturer’s database.

Glasses BH-200, NN-200 GOST 19908.

The glasses are In 1−100−1-250 GOST 25336.

Filters obestochennye (blue ribbon).

The unit with a closed spiral.

The electrodes are platinum mesh according to GOST 6563.

The drying Cabinet of the laboratory.

Nitric acid of high purity according to GOST 11125 and diluted 1:1, 1:2, 1:10.

Hydrochloric acid of high purity according to GOST 14261 and diluted 1:1, 1:2.

Potassium phosphate according to GOST odnosemjannyj 4198 H. h

Potassium dichromate according to GOST 4220, H. h twice recrystallized and dried to constant weight at a temperature of 140−150 °C.

Carbonyl iron or

The iron powder according to GOST 9849.

Cadmium GOST 1467.

Cobalt GOST 123.

Manganese GOST 6008.

Copper according to the GOST 859.

Arsenic metal.

Nickel GOST 849.

Lead according to GOST 3778.

Antimony GOST 1089.

Zinc GOST 3640.

Argon gaseous and liquid GOST 10157.

Tellurium of high purity according to normative-technical documentation.

Standard samples for composition of copper.

3.2. Preparations for the analysis

3.2.1. Preparation of standard solutions of elements according to claim 2.2.1

3.2.2. Preparation of working standard solutions for the method with inductively coupled plasma

Solution 1: in a volumetric flask with a capacity of 100 cmconsistently make pipette 0.3 cmstandard solutions of cadmium, cobalt, manganese, arsenic, antimony, phosphorus, chromium and 1.5 cmstandard solutions of iron, Nickel, lead, zinc, and adjusted to the mark with nitric acid, diluted 1:10.

Solution 2: in a volumetric flask with a capacity of 100 cmconsistently make with a pipette of 1.0 cmstandard solutions of cadmium, cobalt, manganese, arsenic, antimony, phosphorus, chromium and 5.0 cmstandard solutions of iron, Nickel, lead, zinc, and adjusted to the mark with nitric acid, diluted 1:10.

Solution 3: in a volumetric flask with a capacity of 100 cmconsistently contribute pipette 5 cmstandard solutions of cadmium, cobalt, manganese, arsenic, antimony, phosphorus, chromium and 2.5 cmstandard solutions Used iron, Nickel, lead, zinc, adjusted to the mark with nitric acid, diluted 1:10.

Solution 4: in a volumetric flask with a capacity of 100 cmconsistently make with a pipette of 1.0 cmof standard solutions B cadmium, cobalt, manganese, arsenic, antimony, phosphorus, chromium and 5.0 cmstandard solutions Used iron, Nickel, lead, zinc, adjusted to the mark with nitric acid, diluted 1:10.

Working standard solutions of copper

In a volumetric flask with a capacity of 100 cmmake a pipette consistently 5,0; 20; 50 cmstandard solution of copper (according to claim 2.2.1.16) and adjusted to the mark with nitric acid, diluted 1:10. Solutions contain respectively 500, 2000 and 5000 µg/cmof copper.

The mass concentration of the working standard solutions of impurities are given in table.7.

Table 7

3.2.3. Preparation of solutions for validation of correlation coefficients

In a volumetric flask with a capacity of 100 cmpipette consistently contribute 0,0; 5,0; 20.0 and 50.0 cmof a standard solution of copper, prepared according to claim 2.2.1.19.

In each flask with a solution of copper make a 1 cmstandard solution of cadmium, cobalt, arsenic, antimony, and 5 cmstandard solutions of lead, zinc, adjusted to the mark with nitric acid, diluted 1:10. Mass concentration of elements in solutions are given in table.8.

Table 8

3.2.4. Preparation of working standard solutions for atomic absorption method

Solution 1: in a volumetric flask with a capacity of 100 cmconsistently making pipette 1 cmstandard solutions of cadmium, manganese, arsenic, Nickel, lead, antimony, tellurium, and 10 cmof the solution In the cobalt, brought to the mark with nitric acid, diluted 1:10.

Solution 2: in a volumetric flask with a capacity of 100 cmconsistently contribute pipette 5 cmstandard solutions of cadmium, manganese, arsenic, Nickel, lead, antimony, tellurium, chromium and 2.5 cmstandard solution In the cobalt, brought to the mark with nitric acid, diluted 1:10.

Solution 3: in a volumetric flask with a capacity of 100 cmhas consistently poured in 10 cmstandard solutions of cadmium, manganese, arsenic, Nickel, lead, antimony, tellurium, chromium and 0.5 cmstandard solution B of cobalt, adjusted to the mark with nitric acid, diluted 1:10.

Solution 4: in a volumetric flask with a capacity of 100 cmconsistently pour 0.5 cmof standard solutions B, manganese, arsenic, Nickel, lead, antimony, tellurium, chromium and 1 cmstandard solution B of cobalt and is adjusted to the mark with nitric acid, diluted 1:10.

Solution 5: in a volumetric flask with a capacity of 100 cmconsistently pour 0.5 cmof standard solutions B, manganese, arsenic, Nickel, lead, antimony, tellurium, and 1 cmof a solution of chromium, adjusted to the mark with nitric acid, diluted 1:10.

The mass concentration of the working standard solutions of impurities are given in table.9.

Table 9

3.3. Analysis

Weighed samples of copper with a mass of 2,000 g was placed in a quartz glass with a capacity of 200 cm. To remove surface contamination, the sample is washed once with nitric acid, diluted 1:10, and twice — deionized water, draining each time the solution by decantation.

In a glass graduated cylinder pour 18−20 cmof nitric acid, diluted 1:1, purified in a quartz dish, priliva it on the walls of the glass. Cover the beaker quartz cover glass and leave you without heat until the cessation of the violent reaction. Remove the glass, wash it with water over the glass and then weakly heated to dissolve the sample and the complete removal of nitrogen oxides. Then in a glass pour 120−130 cmof water, 12−15 cmof nitric acid and the solution is heated to a temperature of 70−90 °C.

The heated solution is subjected to electrolysis at a voltage of (2,0±0,2) V for 1.5−2 h until a pale blue color of the solution. During the electrolysis the solution in the glass 2−3 times to mix. If the electrodes are covered with bubbles of released gas, they are removed tapping on the electrode. During electrolysis unacceptable circuit of the electrodes.

At the end of the electrolysis without turning off the current, the electrodes are washed with water. Then the current is shut off, the electrodes removed, and the electrolyte is evaporated when heated to wet salts. Salt is dissolved in 4−5 cmof nitric acid, diluted 1:10. The solution is placed in a quartz test tube with a capacity of 10 cmand was adjusted to the mark with nitric acid, diluted 1:10.

3.4. Analysis of atomic emission spectrometer with inductively coupled plasma

3.4.1. The spectrometer is prepared to work in accordance with the manual.

Conditions of measurements in accordance with the table.10.

Table 10

Wavelengths of elements determined are given in table.11.

Table 11

Before making a measurement, specify the previously calculated correction factors for mass concentrations of impurities taking into account the magnitude of the spectral interference from copper. To do this, measure the mass concentration of copper and impurities in the solution prepared according to claim 3.2.3, and if they differ from the given in table.8 more than 20%, the correction factors calculated again.

The capillary spray system is lowered into the test tube with analyzed solution. Before analyzing the next sample capillary spray system is washed with water at 10−15 C. Simultaneously with the analysis of spend control experience for inclusion in the analysis result of the amendment, taking into account the mass fraction of detectable elements in the reagents and materials. The correction is calculated as arithmetic mean of two parallel definitions.

3.4.2. Processing and evaluation of results

3.4.2.1. The calculation of the concentrations of the identified elements is carried out on a computer used by the formula given below.

Mass fraction of the element in the sample of copper () in percent is calculated by the formula

, (7)

where is the mass concentration of the analyzed element in the sample solution, µg/cm;

 — mass concentration of the element in solution in the reference experiment, µ g/cm;

 — the volume of the analyzed solution, cm;

 — weight of copper,

The concentration of each analyzed element in the solution of the control experiment (), µg/cm, calculated by the formula

, (8)

where is the intensity of the spectral line of the element, mV;

, are the coefficients of the regression equation obtained during calibration.

The concentration of the analyzed element in the sample solution (), µg/cm, calculated by the formula

, (9)

where is the intensity of the spectral line of the analyzed element in the sample solution, mV;

 — correction factor that takes into account the magnitude of the spectral interference from copper;

 — the concentration of copper remaining in the sample solution after the electrolysis, µg/cm.

3.4.2.2. The decision about satisfactory convergence of the results of parallel measurements taken in the case that the discrepancy between the results of three parallel measurements does not exceed (with a confidence probability =0,95) of the values calculated by the formula (8)

, (8)

where , are the coefficients;

 — the arithmetic mean of the results of parallel measurements, %.

The coefficients and are given in table.12.

Table 12

Upon receipt of the results of parallel measurements with differences more acceptable, sample analysis is repeated. If you re analysis of this requirement is not met, then repeat sampling.

3.4.2.3. The decision about the satisfactory reproducibility of the analysis take in the case that the discrepancy between the results of the initial and re-analyses (with confidence =0,95) does not exceed the value calculated by the formula (9)

, (9)

where and  — coefficients in accordance with table.12;

 — the arithmetic mean of the results of the analysis, %.

Control of the correctness of the analysis results according to claim 2.3.6.3.

3.5. Analysis on atomic absorption spectrophotometer

3.5.1. The conditions of measurements and preparatory work required to bring the spectrophotometer in working condition — at the user manual for atomic absorption spectrophotometer. Measurement conditions for polarization spectrophotometer, for example, the company «Hitachi» is shown in the table.13.

Table 13

The correct setting of the spectrophotometer to check on the working standard solutions, the concentration of the elements in them are given in table.9.

Stages and conditions of process of atomization of the sample in the electrothermal atomizer is shown in table.14.

Table 14

Temperature for the electrothermal atomizer

Cleaning of cuvettes is carried out at a temperature of 2800 °C for 3 s.

Conduct the atomization of the sample solution and measure the absorption of the resonance lines of the determined elements at the wavelengths given in table.13.

The mass concentration of elements determined by a calibration chart.

Simultaneously with the analysis carried out two test expertise to the amendment in the result of the analysis, taking into account the mass fraction of detectable elements in the reagents, materials. The amendment is calculated as the arithmetic mean of the results of two parallel measurements.

3.5.2. Processing and evaluation of results

Mass fraction of the element () in percent is calculated by the formula

, (10)

where is the concentration of element in the analyzed solution samples, was found in the calibration schedule, µg/cm;

is the concentration of element in solution in the reference experiment, µ g/cm;

 — the volume of the analyzed solution, cm;

 — the weight of the portion of the sample,

The decision about satisfactory convergence of the results of parallel measurements is taken in case if the difference between the highest and lowest results of three parallel measurements at a confidence level =0.95 does not exceed allowable absolute differences calculated by the formula (11)

, (11)

where and  — coefficients are given in table.15;

 — the arithmetic mean of the results of parallel measurements, %.

Table 15

Upon receipt of the results of parallel measurements with differences more acceptable repeat analysis of new batches of copper.

If you re analysis of this requirement is not met, then repeat sampling.

If unsatisfactory re-evaluation for analysis by this technique stops to identify and eliminate the causes of deviation.

The decision about the satisfactory reproducibility of the analysis take in the case that the difference between the initial and repeat tests at a =0.95 does not exceed differences calculated by the formula (12)

, (12)

where and  — coefficients are given in table.15;

 — the arithmetic mean of the results of the analysis, %.

3.5.3 checking the results of the analysis implement according to claim 2.3.6.3.